EP1699557A1 - Catalyseur heterogene a base de ruthenium, procede pour l'hydrogenation d'un groupe aromatique carbocyclique et ethers diglycidyliques a noyau hydrogene des bisphenols a et f - Google Patents

Catalyseur heterogene a base de ruthenium, procede pour l'hydrogenation d'un groupe aromatique carbocyclique et ethers diglycidyliques a noyau hydrogene des bisphenols a et f

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Publication number
EP1699557A1
EP1699557A1 EP04804056A EP04804056A EP1699557A1 EP 1699557 A1 EP1699557 A1 EP 1699557A1 EP 04804056 A EP04804056 A EP 04804056A EP 04804056 A EP04804056 A EP 04804056A EP 1699557 A1 EP1699557 A1 EP 1699557A1
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EP
European Patent Office
Prior art keywords
catalyst
weight
ruthenium
bisglycidyl
hydrogenation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP04804056A
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German (de)
English (en)
Inventor
Jan-Dirk Arndt
Frederik Van Laar
Michael Becker
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
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Filing date
Publication date
Priority claimed from DE2003161151 external-priority patent/DE10361151A1/de
Priority claimed from DE102004055805A external-priority patent/DE102004055805A1/de
Application filed by BASF SE filed Critical BASF SE
Publication of EP1699557A1 publication Critical patent/EP1699557A1/fr
Withdrawn legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/462—Ruthenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/58—Platinum group metals with alkali- or alkaline earth metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
    • C07D303/18—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals
    • C07D303/28—Ethers with hydroxy compounds containing oxirane rings
    • C07D303/30—Ethers of oxirane-containing polyhydroxy compounds in which all hydroxyl radicals are etherified with oxirane-containing hydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C08G59/1405—Polycondensates modified by chemical after-treatment with inorganic compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/08—Silica
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/638—Pore volume more than 1.0 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm

Definitions

  • Ruthenium heterogeneous catalyst process for the hydrogenation of a carbocyclic aromatic group and nuclear hydrogenated bisglycidyl ethers of bisphenols A and F.
  • the present invention relates to a ruthenium heterogeneous catalyst containing silicon dioxide as support material, a process for hydrogenating a carbocyclic aromatic group to the corresponding carbocyclic aliphatic group, in particular a process for the preparation of a bisglycidyl ether of the formula I.
  • cycloaliphatic oxirane compounds I which have no aromatic groups is of particular interest for the production of light and weather-resistant coating systems.
  • such compounds can be prepared by hydrogenation of corresponding aromatic compounds II.
  • the compounds I are therefore also referred to as "core-hydrogenated bisglycidyl ethers of bisphenols A and F".
  • the compounds II have long been known as constituents of coating systems (see JW Muskopf et al. "Epoxy Resins" in Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition on CD-ROM).
  • US Pat. No. 3,336,241 Teaches the hydrogenation of corresponding aromatic epoxy compounds using rhodium and ruthenium catalysts for the preparation of cycloaliphatic compounds having epoxy groups.
  • the activity of the catalysts decreases so much after a hydrogenation that in a technical process the catalyst has to be changed after each hydrogenation.
  • the selectivity of the catalysts described there leaves something to be desired.
  • DE-A-3629632 and DE-A-39 19228 teach the selective hydrogenation of the aromatic molecular parts of bis [glycidyloxiphenyl] methane and of 2,2-bis [p-glycidyloxiphenyl] propane on ruthenium oxide hydrate. This improves the selectivity of the hydrogenation with regard to the aromatic groups to be hydrogenated. According to this teaching, however, it is advisable to regenerate the catalyst after each hydrogenation, the separation of the catalyst from the reaction mixture proving to be problematic.
  • EP-A-678512 (BASF AG) teaches the selective hydrogenation of the aromatic molecular parts of aromatic compounds with oxirane groups on ruthenium catalysts, preferably ruthenium oxide hydrate, in the presence of 0.2 to 10% by weight of water, based on the reaction mixture. Although the presence of water makes it easier to separate the catalyst from the reaction mixture, it does not overcome the other disadvantages of these catalysts, such as the service life that can be improved.
  • EP-A-921 141 and EP-A1-1 270633 relate to the selective hydrogenation of double bonds in certain epoxy compounds in the presence of Rh and / or Ru catalysts with a certain surface or in the presence of catalysts containing metals from the platinum group.
  • JP-A-2002226380 discloses the nuclear hydrogenation of aromatic epoxy compounds in the presence of supported Ru catalysts and a carboxylic acid ester as a solvent.
  • JP-A2-2001 261666 (Maruzen Petrochem.) Relates to a process for the continuous core hydrogenation of aromatic epoxy compounds in the presence of Ru catalysts which are preferably supported on activated carbon or aluminum oxide.
  • JP 10-204002 (Dainippon) relates to the use of specific, in particular alkali metal-doped Ru catalysts in kerhydration processes.
  • JP-A-2002249488 (Mitsubishi) teaches hydrogenation processes in which a noble metal carrier catalyst is used, the chlorine content of which is below 1500 ppm.
  • WO-A1-03 / 103 830 and WO-A1 -04/009526 relate to the hydrogenation of aromatic compounds, in particular the production of alicyclic polycarboxylic acids or their esters by core hydrogenation of the corresponding aromatic polycarboxylic acids or their esters, as well as suitable catalysts.
  • EP-A2-814098 (BASF AG) relates inter alia to Process for the nuclear hydrogenation of organic compounds in the presence of special supported Ru catalysts.
  • WO-A2-02 / 100538 (BASF AG) describes a process for the preparation of certain cycloaliphatic compounds which have side chains with epoxy groups by heterogeneously catalytic hydrogenation of a corresponding compound which has at least one carbocyclic, aromatic group and at least one side chain with at least one Has epoxy group on a ruthenium catalyst.
  • the ruthenium catalyst is available from
  • step ii) is carried out immediately after step i).
  • WO-A2-02 / 100538 teaches that the compounds used can be “both monomeric and oligomeric or polymeric compounds” (page 9 above).
  • WO-A2-02 / 100538 does not teach anything about the addition of alkaline earth metal ions.
  • the present invention had for its object to provide an improved selective process for the hydrogenation of aromatic groups to the corresponding "core-hydrogenated" groups, with the high yields and space-time yields, [product amount / (catalyst volume • time)] (kg / ( l • h)) [amount of product / (reactor volume • time)] (kg / (l Rea kt o r • h)), based on the catalyst used can be achieved and in which the catalysts used, without further treatment several times for hydrogenations can. In particular, longer catalyst service lives should be achieved compared to the process of WO-A2-02 / 100538. Furthermore, bisglycidyl ethers of the formula I with improved properties, in particular in their typical applications, should be found.
  • a ruthenium heterogeneous catalyst containing silicon dioxide as a support material which is characterized in that the catalyst surface contains alkaline earth metal ions (M + ), a process for hydrogenating a carbocyclic aromatic group to the corresponding carbocyclic aliphatic group, in particular a process for the preparation of the bisglycidyl ethers of the formula I
  • An essential component of the catalysts according to the invention is the support material based on amorphous silicon dioxide.
  • amorphous means that the proportion of crystalline silicon dioxide phases makes up less than 10% by weight of the carrier material.
  • the support materials used to produce the catalysts can, however, have superstructures which are formed by regular arrangement of pores in the support material.
  • M 2+ alkaline earth metal ions
  • amorphous silicon dioxide types which consist of at least 90% by weight silicon dioxide come into consideration as carrier materials, the remaining 10% by weight, preferably not more than 5% by weight, of the carrier material also being another oxidic material can, for example MgO, CaO, TiO 2 , ZrO 2 , Fe 2 O 3 and / or alkali metal oxide.
  • the carrier material is halogen-free, in particular chlorine-free, i.e. H.
  • the content of halogen in the carrier material is less than 500 ppm by weight, e.g. in the range of 0 to 400 ppm by weight.
  • Support materials are preferred which have a specific surface area in the range from 30 to 700 m 2 / g, preferably 30 to 450 m 2 / g, (BET surface area in accordance with DIN 66131).
  • Suitable amorphous support materials based on silicon dioxide are familiar to the person skilled in the art and are commercially available (see, for example, O.W. Flörke, "Silica” in Ullmann's Encyclopedia of Industrial Chemistry 6th Edition on CD-ROM). They can be of natural origin as well as artificially produced.
  • suitable amorphous carrier materials based on silicon dioxide are silica gels, diatomaceous earth, pyrogenic silicas and precipitated silicas.
  • the catalysts have silica gels as support materials.
  • the carrier material can have different shapes.
  • the support material in the form of a finely divided powder will usually be used to produce the catalysts according to the invention.
  • the powder preferably has particle sizes in the range from 1 to 200 ⁇ m, in particular 1 to 100 ⁇ m.
  • moldings made from the support material are usually used, for example by extrusion, extrusion or tableting are available and which can have the shape of balls, tablets, cylinders, strands, rings or hollow cylinders, stars and the like, for example.
  • the dimensions of these moldings usually range from 1 mm to 25 mm. Catalyst strands with strand diameters of 1.5 to 5 mm and strand lengths of 2 to 25 mm are frequently used.
  • the content of ruthenium in the catalysts can be varied over a wide range. It will preferably be at least 0.1% by weight, preferably at least 0.2% by weight, and often will not exceed a value of 10% by weight, in each case based on the weight of the support material and calculated as elemental ruthenium. Preferably the ruthenium content is in the range of 0.2 to 7% by weight and in particular in the range of 0.4 to 5% by weight, e.g. 1.5 to 2% by weight.
  • the content of alkaline earth metal ions (M 2+ ) in the catalyst surface is preferably 0.01 to 1% by weight, in particular 0.05 to 0.5% by weight, very particularly 0.1 to 0.25 % By weight, in each case based on the weight of the silicon dioxide carrier material.
  • the ruthenium catalysts according to the invention are preferably prepared by first treating the support material with a solution of a low molecular weight ruthenium compound, hereinafter referred to as (ruthenium) precursor, in such a way that the desired amount of ruthenium is absorbed by the support material.
  • Preferred solvents here are glacial acetic acid, water or mixtures thereof. This step is also referred to below as watering.
  • the carrier treated in this way is then dried, preferably in compliance with the upper temperature limits specified below. If necessary, the solid thus obtained is then treated again with the aqueous solution of the ruthenium precursor and dried again. This process is repeated until the amount of ruthenium compound taken up by the support material corresponds to the desired ruthenium content in the catalyst.
  • the treatment or impregnation of the carrier material can take place in different ways and depends in a known manner on the shape of the carrier material.
  • the carrier material can be sprayed or rinsed with the precursor solution or the carrier material can be suspended in the precursor solution.
  • the support material can be suspended in the aqueous solution of the ruthenium precursor and filtered off from the aqueous supernatant after a certain time.
  • the ruthenium content of the catalyst can then be controlled in a simple manner via the amount of liquid taken up and the ruthenium concentration of the solution.
  • the support material can also be impregnated, for example, by treating the support with a defined amount of the solution of the ruthenium precursor that corresponds to the maximum amount of liquid that the support material can hold.
  • the carrier material can be sprayed with the required amount of liquid.
  • suitable apparatus for this are those commonly used for mixing liquids with solids Apparatus (see Vauck / Müller, basic operations of chemical process engineering, 10th edition, German publisher for basic material industry, 1994, p. 405 ff.), For example tumble dryers, water drums, drum mixers, paddle mixers and the like.
  • Monolithic supports are usually rinsed with the aqueous solutions of the ruthenium precursor.
  • the solutions used for impregnation are preferably low in halogen, especially low in chlorine, ie they contain no or less than 500 ppm by weight, in particular less than 100 ppm by weight of halogen, for example 0 to ⁇ 80 ppm by weight of halogen, based on the total weight the solution.
  • halogen especially low in chlorine
  • ruthenium compounds which do not contain chemically bound halogen and which are sufficiently soluble in the solvent are therefore preferably used as ruthenium precursors.
  • Ru (III) acetate is a particularly preferred Ru precursor. This Ru compound is usually dissolved in acetic acid or glacial acetic acid, but it can also be used as a solid.
  • the catalyst according to the invention can be produced without using water.
  • ruthenium precursors are offered commercially as a solution, but the matching solids can also be used. These precursors can either use the same component as the solvent offered, e.g. Nitric acid, acetic acid, hydrochloric acid, or preferably dissolved or diluted with water. Mixtures of water or solvent with up to 50% by volume of one or more organic solvents miscible with water or solvent, e.g. Mixtures with d-C alkanols such as methanol, ethanol, n-propanol or isopropanol can be used. All mixtures should be chosen so that there is a solution or phase. The concentration of the ruthenium precursor in the solutions naturally depends on the amount of ruthenium precursor to be applied and the absorption capacity of the support material for the solution and is preferably in the range from 0.1 to 20% by weight.
  • Drying can be carried out according to the usual methods of drying solids while observing the temperature limits specified below. Compliance with the upper limit of the drying temperatures is important for the quality, ie the activity of the catalyst. Exceeding the drying temperatures given below leads to a significant loss of activity. Calcining the support at higher temperatures, for example above 300 ° C. or even 400 ° C., as is proposed in the prior art, is not only superfluous but also has a disadvantageous effect on the activity of the catalyst. To achieve adequate drying speeds, drying is preferably carried out at elevated temperature, preferably at 180 180 ° C, particularly at ⁇ 160 ° C, and at at least 40 ° C, in particular at least 70 ° C, especially at least 100 ° C, very particularly at least 140 ° C.
  • the drying of the solid impregnated with the ruthenium precursor usually takes place under normal pressure, and a reduced pressure can also be used to promote drying. Often, to promote drying, a gas stream is passed over or through the material to be dried, for example air or nitrogen.
  • the drying time naturally depends on the desired degree of drying and the drying temperature and is preferably in the range from 1 h to 30 h, preferably in the range from 2 to 10 h.
  • the treated carrier material is preferably dried to such an extent that the content of water or volatile solvent components before the subsequent reduction is less than 5% by weight, in particular not more than 2% by weight, based on the total weight of the solid.
  • the weight percentages here relate to the weight loss of the solid, determined at a temperature of 160 ° C., a pressure of 1 bar and a duration of 10 minutes. In this way, the activity of the catalysts used according to the invention can be increased further.
  • Drying is preferably carried out by moving the solid treated with the precursor solution, for example by drying the solid in a rotary tube oven or a rotary ball oven. In this way, the activity of the catalysts according to the invention can be increased further.
  • the solid obtained after drying is converted into its catalytically active form by reducing the solid at the temperatures indicated above in a manner known per se.
  • the carrier material is brought into contact with hydrogen or a mixture of hydrogen and an inert gas at the temperatures given above.
  • the absolute hydrogen pressure is of minor importance for the result of the reduction and is e.g. can be varied in the range from 0.2 bar to 1.5 bar.
  • the hydrogenation of the catalyst material often takes place at normal hydrogen pressure in a hydrogen stream.
  • the reduction is preferably carried out by moving the solid, for example by reducing the solid in a rotary tube furnace or a rotary ball furnace. In this way, the activity of the catalysts according to the invention can be increased further.
  • the reduction can also be carried out using organic reducing reagents such as hydrazine, formaldehyde, formates or acetates.
  • the catalyst can be passivated in a known manner in order to improve the manageability, for example by briefly using the catalyst with an oxygen-containing gas, for example air, but preferably with a 1 to 10 vol .-% oxygen-containing inert gas mixture treated. CO 2 or CO 2 / O 2 mixtures can also be used here.
  • an oxygen-containing gas for example air
  • CO 2 or CO 2 / O 2 mixtures can also be used here.
  • the active catalyst can also be used under an inert organic solvent, e.g. Ethylene glycol.
  • the ruthenium catalyst precursor e.g. as prepared above or as described in WO-A2-02 / 100538 (BASF AG), impregnated with a solution of one or more alkaline earth metal (II) salts.
  • Preferred alkaline earth metal (II) salts are corresponding nitrates, such as, in particular, magnesium nitrate and calcium nitrate.
  • the preferred solvent for the alkaline earth metal (II) salts in this impregnation step is water.
  • the concentration of the alkaline earth metal (II) salt in the solvent is e.g. 0.01 to 1 mol / liter.
  • the Ru / SiO 2 catalyst installed in a tube is contacted with a stream of an aqueous solution of the alkaline earth metal salt.
  • the catalyst to be impregnated can also be treated with a supernatant solution of the alkaline earth metal salt.
  • the Ru / SiO 2 catalyst in particular its surface, is thus preferably saturated with the alkaline earth metal ion (s).
  • the catalyst according to the invention can be dried after impregnation.
  • the drying can e.g. in an oven at ⁇ 200 ° C, e.g. at 50 to 190 ° C, particularly preferably at ⁇ 140 ° C, e.g. B. at 60 to 130 ° C, are carried out.
  • This impregnation process can be carried out ex situ or in situ: ex situ means before the catalyst is installed in the reactor, in situ means in the reactor (after the catalyst has been installed).
  • the impregnation of the catalyst surface with alkaline earth metal ions can also take place in situ by adding alkaline earth metal ions, for example in the form of dissolved alkaline earth metal salts, to the solution of the aromatic substrate (educt) to be hydrogenated.
  • alkaline earth metal ions for example in the form of dissolved alkaline earth metal salts
  • the appropriate amount of salt first dissolved in water and then added to the substrate dissolved in an organic solvent.
  • the content of alkaline earth metal ions in the solution of the aromatic substrate to be hydrogenated is generally 1 to 100 ppm by weight, in particular 2 to 10 ppm by weight.
  • the catalyst according to the invention is used in combination with an alkaline earth metal ion-containing solution of the aromatic substrate to be hydrogenated.
  • the ruthenium is present in the catalysts according to the invention as metallic ruthenium. Electron microscopic investigations (SEM or TEM) have also shown that there is a coated catalyst: the ruthenium concentration within a catalyst grain decreases from the outside inwards, with a ruthenium layer on the grain surface. In preferred cases, crystalline ruthenium can be detected in the shell using SAD (Selected Area Diffraction) and XRD (X-Ray Diffraction).
  • the halide content, in particular chloride content, of the catalysts according to the invention is also below 0.05% by weight (0 to ⁇ 500 ppm by weight, for example in the range from 0 to 400 Ppm by weight), based on the total weight of the catalyst.
  • the chloride content is e.g. determined by ion chromatography using the method described below.
  • the percentage ratio of the Q 2 and Q 3 structures Q 2 / Q 3 determined by means of 29 Si solid-state NMR is less than 25, preferably less than 20, particularly preferably less than 15, for example is in the range of 0 to 14 or 0.1 to 13. This also means that the degree of condensation of the silica in the carrier used is particularly high.
  • the carrier material preferably contains not more than 1% by weight and in particular not more than 0.5% by weight and in particular ⁇ 500% by weight of aluminum oxide, calculated as Al 2 O 3 .
  • the total concentration of Al (III) and Fe (II and / or III) is preferably less than 300 ppm, particularly preferably less than 200 ppm, and is e.g. in the range of 0 to 180 ppm.
  • the proportion of alkali metal oxide preferably results from the production of the carrier material and can be up to 2% by weight. It is often less than 1% by weight. Alkali metal oxide-free supports (0 to ⁇ 0.1% by weight) are also suitable.
  • the proportion of MgO, CaO, TiO 2 or ZrO 2 can make up to 10% by weight of the carrier material and is preferably not more than 5% by weight. However, carrier materials which do not contain any detectable amounts of these metal oxides (0 to ⁇ 0.1% by weight) are also suitable.
  • the carbocyclic aromatic group in the organic compound to be hydrogenated is in particular a benzene ring which can carry substituents.
  • Bisphenol A or bisphenol F or comparable compounds can be reacted with epichlorohydrin and bases in a known manner (for example Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, VCH (1987), Vol. A9, p. 547) to give glycidyl ether of the general formula IIIa become,
  • R 2 represents hydrogen or a C 1 -C 4 -alkyl group, for example methyl, or two radicals R 2 bonded to a carbon atom form a C -C 5 -alkylene group and m represents zero to 40.
  • Novolaks of the general formula Mb can be obtained by acid-catalyzed reaction of phenol or cresol and conversion of the reaction products to the corresponding glycidyl ethers (see e.g. bis [4- (2,3-epoxypropoxy) phenyl] methane):
  • R 2 is hydrogen or a methyl group and n is 0 to 40 (see JW Muskopf et al. "Epoxy Resins 2.2.2" in Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition on CD-ROM).
  • Glycidyl ethers of reaction products from phenol and an aldehyde Acid-catalyzed reaction of phenol and aldehydes and subsequent reaction with epichlorohydrin make glycidyl ethers accessible, e.g. 1,1,2,2-tetrakis [4- (2,3-epoxypropoxy) phenyl] ethane is available from phenol and glyoxal (see JW Muskopf et al. "Epoxy Resins 2.2.3" in Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition on CD-ROM).
  • Glycidyl ethers of phenol hydrocarbon novolacs e.g. 2,5- bis [(glycidyloxy) phenyl] octahydro-4,7-methano-5H-indene and its oligomers.
  • Exemplary are the triglycidyl compound of p-aminophenol, 1- (glycidyloxy) -4- [N, N-bis (glycidyl) amino] benzene, and the tetragiycidyl compound of methylenediamine bis ⁇ 4- [N, N-bis (2, 3-epoxypropyl) amino] phenyl ⁇ methane to name.
  • R is CH 3 or H, is nuclear hydrogenated.
  • Aromatic bisglycidyl ethers of the formula II which are preferably used have a chloride and / or organically bound chlorine content of 1000 1000 ppm by weight, particularly ⁇ 950 ppm by weight, in particular in the range from 0 to ⁇ 800 ppm by weight, e.g. 600 to 1000 ppm by weight.
  • the chloride and / or organically bound chlorine content is e.g. determined using the methods described below by ion chromatography or coulometry.
  • the aromatic bisglycidyl ether of the formula II used has a content of corresponding oligomeric bisglycidyl ethers of less than 10% by weight, in particular less than 5% by weight. %, particularly less than 1.5% by weight, very particularly less than 0.5% by weight, for example in the range from 0 to ⁇ 0.4% by weight.
  • the oligomer content in the feed has a decisive influence on the service life of the catalyst, i.e. sales remain at a high level for longer.
  • a slower catalyst deactivation is observed.
  • the oligomer content of the aromatic bisglycidyl ethers of formula II used is preferably determined by means of GPC measurement (Gel Permeation Chromatography) or by determining the evaporation residue.
  • the evaporation residue is determined by heating the aromatic bisglycidyl ether for 2 h at 200 ° C and for a further 2 h at 300 ° C at 3 mbar.
  • the corresponding oligomeric bisglycidyl ethers generally have a molecular weight determined by GPC measurement in the range from 380 to 1500 g / mol and have e.g. the following structures (see e.g. Journal of Chromatography 238 (1982), pages 385-398, page 387):
  • R CH 3 or H.
  • n 1, 2, 3 or 4.
  • the oligomers can be separated off e.g. by means of chromatography or on a larger scale, preferably by distillation, e.g. on a laboratory scale in a batch distillation or on an industrial scale in a thin-film evaporator, preferably in a short-path distillation, in each case under vacuum.
  • Batch distillation for oligomer separation is e.g. at a pressure of 2 mbar the bath temperature at approx. 260 ° C and the transition temperature at the head at approx. 229 ° C.
  • the oligomer removal can also be carried out under milder conditions, for example under reduced pressures in the range from 1 to 10 '3 mbar.
  • the boiling temperature of the oligomer-containing feedstock decreases by 20-30 ° C depending on the feedstock and thus also the thermal product load.
  • the distillation is preferably carried out in a continuous procedure in a thin-film evaporation or particularly preferably in a short-path evaporation.
  • the starting materials are hydrogenated, e.g. of the compounds II, preferably in the liquid phase.
  • the hydrogenation can be carried out without solvent or in an organic solvent. Due to the partially high viscosity of the compounds II, they will preferably be used as a solution or mixture in an organic solvent.
  • Suitable organic solvents are in principle those which are able to dissolve the starting material, for example the compound II, as completely as possible or mix completely with it and which are inert under the hydrogenation conditions, ie are not hydrogenated.
  • suitable solvents are cyclic and acyclic ethers, for example tetrahydrofuran, dioxane, methyl tert-butyl ether, dimethoxyethane, dimethoxypropane, dimethyldiethylene glycol, aliphatic alcohols such as methanol, ethanol, n- or isopropanol, n-, 2 -, Iso- or tert-butanol, carboxylic acid esters such as methyl acetate, ethyl acetate, propyl acetate or butyl acetate, and aliphatic ether alcohols such as methoxypropanol.
  • the concentration of starting material, e.g. of compound II in the liquid phase to be hydrogenated can in principle be chosen freely and is frequently in the range from 20 to 95% by weight, based on the total weight of the solution / mixture. If the reactants are sufficiently free-flowing under the reaction conditions, the hydrogenation can also be carried out in the absence of a solvent.
  • the proportion of water, based on the mixture to be hydrogenated can be up to 10% by weight, e.g. 0.1 to 10% by weight, preferably 0.2 to 7% by weight and in particular 0.5 to 5% by weight.
  • the actual hydrogenation is usually carried out in analogy to the known hydrogenation processes, as described in the prior art mentioned at the beginning.
  • the starting material e.g. the compound II, preferably as a liquid phase
  • the catalyst can either be suspended in the liquid phase (suspension mode) or the liquid phase is passed over a fluidized catalyst bed (fluidized bed mode) or a fixed catalyst bed (fixed bed mode).
  • the hydrogenation can be carried out either continuously or batchwise.
  • the process according to the invention is preferably carried out in trickle reactors according to the fixed bed procedure.
  • the hydrogen can be passed both in cocurrent with the solution of the starting material to be hydrogenated and in countercurrent over the catalyst.
  • Suitable apparatus for carrying out a hydrogenation according to the suspension procedure as well as for hydrogenation on the catalyst fluidized bed and on the fixed catalyst bed are known from the prior art, e.g. from Ullmann's Encyclopedia of Technical Chemistry, 4th Edition, Volume 13, pp. 135 ff., and from P. N. Rylander, "Hydrogenation and Dehydrogenation” in Ullmann's Encyclopedia of Industrial Chemistry, 5th ed. on CD-ROM.
  • the hydrogenation according to the invention can be carried out both at normal hydrogen pressure and at elevated hydrogen pressure, for example at a hydrogen absolute pressure of at least 1.1 bar, preferably at least 10 bar.
  • the absolute hydrogen pressure will not exceed 325 bar and preferably 300 bar.
  • the hydrogen absolute pressure is particularly preferably in the range from 20 to 300 bar, for example in the range from 50 to 280 bar.
  • the reaction temperatures in the process according to the invention are generally at least 30 ° C. and will often not exceed 200 ° C.
  • the hydrogenation process is carried out at temperatures in the range from 40 to 150 ° C., for example from 40 to 100 ° C., and particularly preferably in the range from 45 to 80 ° C.
  • reaction gases also include hydrogen-containing gases which do not contain any catalyst poisons such as carbon monoxide or sulfur-containing gases, e.g. Mixtures of hydrogen with inert gases such as nitrogen or reformer exhaust gases, which usually still contain volatile hydrocarbons. Pure hydrogen is preferably used (purity 99 99.9% by volume, particularly 99 99.95% by volume, in particular 99 99.99% by volume).
  • the starting material to be hydrogenated is usually added in an amount of 0.05 to 3 kg / (l (catalyst) " h), in particular 0.15 to 2 kg / (l (catalyst)" h) lead the catalyst.
  • the catalysts used in this process can of course be regenerated according to the methods known to those skilled in the art for noble metal catalysts such as ruthenium catalysts.
  • the treatment of the catalyst with oxygen as described in BE 882279 the treatment with dilute, halogen-free mineral acids as described in US Pat. No. 4,072,628, or the treatment with hydrogen peroxide, e.g. B. in the form of aqueous solutions with a content of 0.1 to 35 wt .-%, or the treatment with other oxidizing substances, preferably in the form of halogen-free solutions.
  • a solvent e.g. B. water, rinse.
  • the hydrogenation process according to the invention is preferred through the complete hydrogenation of the aromatic nuclei of the bisglycidyl ether of formula II used
  • R is CH 3 or H, characterized, the degree of hydrogenation being> 98%, particularly> 98.5%, very particularly> 99%, for example> 99.3%, in particular> 99.5%, for example in the range from> 99.8 to 100%.
  • the degree of hydrogenation (Q) is defined according to
  • the ratio, for example molar ratio, of the cycloaliphatic and aromatic C6 rings can preferably be determined by means of 1 H-NMR spectroscopy (integration of the aromatic and correspondingly cycloaliphatic 1 H signals).
  • the invention also relates to bisglycidyl ethers of the formula
  • R is CH 3 or H
  • R is CH 3 or H
  • the bisglycidyl ethers of the formula I preferably have a content of corresponding oligomerically hydrogenated bisglycidyl ethers of the formula
  • R is 3 or H
  • n 1, 2, 3 or 4
  • 10% by weight particularly less than 5% by weight, in particular less than 1.5% by weight, very particularly less than 0.5% by weight, for example in the range from 0 to ⁇ 0.4% by weight.
  • the content of oligomeric, core-hydrogenated bisglycidyl ethers is preferably determined by heating the aromatic bisglycidyl ether for 2 h to 200 ° C. and for a further 2 h to 300 ° C. at 3 mbar in each case or by means of GPC measurement (gel permeation chromatography). For the other respective conditions for determining the oligomer content, see below.
  • the bisglycidyl ethers of the formula I preferably have a total chlorine content, determined according to DIN 51408, of less than 1000 ppm by weight, in particular less than 800 ppm by weight, very particularly less than 600 ppm by weight, e.g. in the range of 0 to 400 ppm by weight.
  • the bisglycidyl ethers of the formula I preferably have a ruthenium content, determined by mass spectrometry with inductively coupled plasma (ICP-MS), of less than 0.3 ppm by weight, in particular less than 0.2 ppm by weight, very particularly less than 0.1% by weight. ppm, e.g. in the range of 0 to 0.09 ppm by weight.
  • ICP-MS inductively coupled plasma
  • the bisglycidyl ethers of the formula I preferably have a platinum-cobalt color number (APHA color number), determined according to DIN ISO 6271, of less than 30, particularly less than 25, very particularly less than 20, e.g. in the range from 0 to 18.
  • APHA color number platinum-cobalt color number
  • the bisglycidyl ethers of the formula I preferably have epoxy equivalents determined in accordance with the ASTM-D-1652-88 standard in the range from 170 to 240 g / equivalents, in particular in the range from 175 to 225 g / equivalents, very particularly in the range from 180 to 220 g / equivalents.
  • the bisglycidyl ethers of the formula I preferably have a proportion of hydrolyzable chlorine, determined according to DIN 53188, of less than 500 ppm by weight, particularly less than 400 ppm by weight, very particularly less than 350 ppm by weight, e.g. in the range from 0 to 300 ppm by weight.
  • the bisglycidyl ethers of the formula I preferably have a kinematic viscosity, determined according to DIN 51562, of less than 800 mm 2 / s, particularly less than 700 mm 2 / s, very particularly less than 650 mm 2 / s, for example in the range from 400 to 630 mm 2 / s , each at 25 ° C.
  • the bisglycidyl ethers of the formula I preferably have a cis / cis: cis / trans: trans / trans isomer ratio in the range from 44-63%: 34-53%: 3-22%.
  • the cis / cis: cis / trans: trans / trans isomer ratio is particularly preferably in the range from 46-60%: 36-50%: 4-18%.
  • the cis / cis: cis / trans: trans / trans isomer ratio is very particularly preferably in the range from 48-57%: 38-47%: 5-14%.
  • the cis / cis: cis / trans: trans / trans isomer ratio is in the range from 51 -56%: 39-44%: 5-10%.
  • the bisglycidyl ethers of the formula I are particularly preferred by complete hydrogenation of the aromatic nuclei of a bisglycidyl ether of the formula II
  • R is CH 3 or H
  • the degree of hydrogenation being> 98%, particularly> 98.5%, very particularly> 99%, for example> 99.3%, in particular> 99.5%, for example in the range from> 99.8 to 100%.
  • catalysts 1 to 3 Preparation of catalysts 1 to 3 according to the invention A defined amount of the support material was placed in a dish and soaked in 90-95% of the amount of a solution of Ru (III) acetate (about 5% Ru in 100% acetic acid) in water maximum of the carrier material can be absorbed.
  • the ruthenium concentration within a catalyst grain of the catalyst decreases from the outside inwards, an Ru layer of up to approximately 200 nm being present on the grain surface. Inside the catalyst grain, the Ru particles are up to approx. 2 nm in size. Below the ruthenium shell, aggregated and / or agglomerated Ru particles are observed in places. In this area, the size of the Ru individual particles is up to approx. 4 nm. Crystalline ruthenium is detected in the shell using SAD.
  • XRD analysis shows a ruthenium crystallite size of approx. 8 nm.
  • the pore volume was determined by means of nitrogen sorption in accordance with DIN 66131.
  • Catalyst 1 Catalyst 2 on catalyst 3 on the same cat.
  • B based on Davicat ® base C15 WO-A-S557 (Grace) 02/100538 (3 mm strands)
  • the carrier of catalyst A from WO 02/100538 corresponds to the carrier of catalyst B from WO 02/100538 (same chemical composition), with the difference that the BET surface area is 68 m 2 / g and the pore volume is 0.8 ml / g is.
  • catalysts 1 to 3 are each impregnated with a Mg 2+ salt solution, for example with an 80 mM (millimolar) aqueous Mg (NO 3 ) 2 solution at room temperature, for example for 15 minutes.
  • the impregnated catalyst is rinsed with water and dried at 80 ° C.
  • the catalyst was produced in accordance with WO-A2-02 / 100538.
  • the carrier was placed in a bowl and soaked in a Ru acetate solution with 95% water absorption. The soaked product was dried at 120 ° C overnight.
  • the reduction was carried out for 2 h at 300 ° C. in a stream of hydrogen at normal pressure in a rotary kiln. After cooling and inerting (N 2 ), the catalyst was passivated at room temperature with dilute air.
  • Catalyst B (with Mg impregnation, according to the invention)
  • Catalyst A (20% by weight) was impregnated with 80% by weight of an 82.5 mM Mg solution (Mg (NO 3 ) 2 • 6 H 2 O) for 15 minutes at room temperature. The impregnated catalyst was rinsed with water and dried at 80 ° C.
  • the conversion and the degree of hydrogenation were determined by 1 H-NMR: sample amount: 20-40 mg, solvent: CDCI 3 , 700 ⁇ liter with TMS as reference signal, sample tube: 5 mm diameter, 400 or 500 MHz, 20 ° C; Decrease in aromatic proton signals vs. Increase in the signals of the aliphatic protons).
  • the conversion indicated in the examples is based on the hydrogenation of the aromatic groups.
  • the decrease in the epoxy groups was determined by comparing the epoxy equivalent (EEW) before and after the hydrogenation, determined in each case according to the ASTM-D-1652-88 standard.
  • Ru catalyst A is a powerful hydrogenation contact for aromatic bisglycidyl ethers. 2. Impregnation of the catalyst with a magnesium salt (contact B) does not change activity or selectivity, but increases stability considerably.
  • a heated reaction tube made of stainless steel (length 0.8 m; diameter 12 mm) filled with 75 ml of catalyst A was used as the reactor, which was equipped with a feed pump for the educt and a separator with maintenance for sampling and exhaust gas control.
  • a 30% by weight solution of 2,2-di- [p-glycidoxiphenyl] propane (distilled product, EEW 171) in THF, which contained 3% by weight of water, was initially used in the hydrogenation.
  • the hydrogenation was carried out at a catalyst load of 0.15 kg / l ⁇ at . # h, an inlet / circulation ratio of 8, a temperature of 50 ° C and a hydrogen pressure of 250 bar.
  • the reactor was operated at the bottom.
  • the example shows: When using a worn Ru contact like catalyst A in a continuous mode of operation, the contact shows leaching and is therefore in need of improvement in terms of an economical technical process.
  • the example shows: 1.
  • the Mg impregnation means that the worn Ru contact, as shown in the batch test, gains considerable stability even in continuous operation (balance 1-7). 2. After some time (-208 hours) a slight Ru-Leaching can be observed (balance 8-9). The cause is probably the washing out of the magnesium. 3. This can be counteracted by adding a small amount of Mg salt to the feed (10-14). The Ru content in the discharge can thus be kept ⁇ 0.1 ppm. 4. Under these conditions, a 40% by weight BGE solution can also be easily hydrogenated (balance 15-20). 5. However, if the amount of Mg added is reduced significantly below 5 ppm (2.5 or 1.25 ppm), slight (0.9 ppm) or strong (1.4 ppm) leaching can be observed again (balance 21 -28).
  • oligomer content in the feed has an influence on the service life of the catalyst:
  • low-oligomer feed
  • oli- slower catalyst deactivation was observed.
  • the oligomer content can e.g. can be determined by means of GPC measurement (Gel Permeation Chromatography):
  • Calibration MG 500-10000000 g / mol with PS calibration kit from Polymer Laboratories.
  • oligomer range ethylbenzene / 1,3-diphenylbutane / 1,3,5-triphenylhexane / 1,3,5,7-tetraphenyloctane / 1,3,5,7,9-pentaphenyl decane.
  • Evaluation limit 180 g / mol.
  • the oligomer content in area% (area%) determined by means of GPC measurement can be converted into% by weight using an internal or external standard.
  • the residue (oligomer content) determined by means of this method in standard goods was 6.1% by weight.
  • the residue (oligomer content) in distilled standard goods determined by this method was 0% by weight. (Distillation conditions: 1 mbar, bath temperature 260 ° C and transition temperature at the top 229 ° C).
  • the hydrogenation of the bisphenol A unit of the bisglycidyl ether can produce several isomers. Depending on the arrangement of the substituents on the cyclohexane rings, cis / cis, trans / trans or cis / trans isomerism can occur. To identify the three isomers, the products of the peaks in question were preparatively collected using a column switch. Each fraction was then characterized by NMR spectroscopy ( 1 H, 13 C, TOCSY, HSQC).
  • the sample was diluted by a factor of 100 with a suitable organic solvent (e.g. NMP).
  • a suitable organic solvent e.g. NMP
  • the ruthenium content in this solution was determined by mass spectrometry with inductively coupled plasma (ICP-MS).
  • ICP-MS spectrometer e.g. Agilent 7500s Measurement conditions: Calibration: External calibration in an organic matrix Atomizer: Meinhardt Mass: Ru102 The calibration line was chosen so that the necessary delivery value could be determined reliably in the diluted measuring solution.
  • Chloride was determined by ion chromatography.
  • Sample preparation Approx. 1 g of the sample was dissolved in toluene and extracted with 10 ml ultrapure water.
  • the aqueous phase was measured by means of ion chromatography.
  • the sample was burned in an oxygen atmosphere at a temperature of approx. 1020 ° C.
  • the chlorine bound in the sample is converted to hydrogen chloride.
  • the nitrous gases, sulfur oxides and water generated during the combustion are removed and the combustion gas cleaned in this way is introduced into the coulometer cell.
  • the coulometric determination of the chloride formed is carried out here according to Cr + Ag + ⁇ AgCI. Weighing range: 1 to 50 mg

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Abstract

L'invention concerne un catalyseur hétérogène à base de ruthénium qui contient du dioxyde de silicium comme matériau support, la surface du catalyseur contenant des ions de métaux alcalino-terreux (M<2+>). L'invention concerne également des procédés pour l'hydrogénation d'un groupe aromatique carbocyclique en groupe aliphatique carbocyclique correspondant. L'invention concerne notamment un procédé pour produire des éthers diglycidyliques de formule (I), dans laquelle R représente CH3 ou H, par hydrogénation du noyau de l'éther diglycidylique aromatique correspondant de formule (II) en utilisant le catalyseur hétérogène à base de ruthénium selon l'invention. L'invention concerne en outre des éthers diglycidyliques de formule (I) produits selon le procédé de l'invention.
EP04804056A 2003-12-22 2004-12-18 Catalyseur heterogene a base de ruthenium, procede pour l'hydrogenation d'un groupe aromatique carbocyclique et ethers diglycidyliques a noyau hydrogene des bisphenols a et f Withdrawn EP1699557A1 (fr)

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DE2003161151 DE10361151A1 (de) 2003-12-22 2003-12-22 Ruthenium-Heterogenkatalysator und Verfahren zur Hydrierung einer carbocyclischen aromatischen Gruppe, insbesondere zur Herstellung eines Bisglycidylethers der Formel I
DE102004055805A DE102004055805A1 (de) 2004-11-18 2004-11-18 Ruthenium-Heterogenkatalysator, Verfahren zur Hydrierung einer carbocyclischen aromatischen Gruppe und kernhydrierte Bisglycidylether der Bisphenole A und F
PCT/EP2004/014455 WO2005061106A1 (fr) 2003-12-22 2004-12-18 Catalyseur heterogene a base de ruthenium, procede pour l'hydrogenation d'un groupe aromatique carbocyclique et ethers diglycidyliques a noyau hydrogene des bisphenols a et f

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DE102005003116A1 (de) * 2005-01-21 2006-07-27 Basf Ag Zusammensetzung enthaltend einen hydrierten Bisglycidylether und ein Vernetzungsmittel
DE102005027567A1 (de) 2005-06-14 2006-12-21 Basf Ag Verfahren zum Passivieren von metallischen Oberflächen mit Säuregruppen aufweisenden Polymeren
DE102005029200A1 (de) 2005-06-22 2006-12-28 Basf Ag Katalysator und Verfahren zur Hydrierung von hydrierbare Gruppen enthaltenden organischen Verbindungen
WO2006136569A1 (fr) * 2005-06-22 2006-12-28 Basf Aktiengesellschaft Catalyseur heterogene au ruthenium et procede pour hydrater un groupe carbocyclique aromatique, en particulier pour preparer des bisglycidylethers a noyau hydrate des bisphenols a et f
US8895791B2 (en) * 2006-07-31 2014-11-25 Basf Se Method of regenerating ruthenium catalysts suitable for hydrogenation
WO2008015170A2 (fr) * 2006-07-31 2008-02-07 Basf Se Procédé de régénération de catalyseurs de ruthénium utilisés pour l'hydrogénation de benzène
US8450534B2 (en) 2010-03-24 2013-05-28 Basf Se Process for preparing 4-cyclohexyl-2-methyl-2-butanol
BR112012022949B1 (pt) 2010-03-24 2020-01-14 Basf Se processo para preparar 4-cicloexil-2-metil-2-butanol, composição, processo para preparar uma composição, uso de 2-metil-4-fenil-2-pentanol ou de uma composição, composto, processo para preparar 4-cicloexil-2-metil-2-pentanol, e, uso de 4-cicloexil-2-metil-2-pentanol ou de uma composição
US9056812B2 (en) 2011-09-16 2015-06-16 Basf Se Process for preparing 4-cyclohexyl-2-methyl-2-butanol
CN103796980B (zh) 2011-09-16 2016-08-31 巴斯夫欧洲公司 制备4-环己基-2-甲基-2-丁醇的方法
US9827554B2 (en) * 2012-09-21 2017-11-28 Jx Nippon Oil & Energy Corporation Fischer-tropsch synthesis catalyst, method for producing same, and method for producing hydrocarbon
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